The present invention relates to a continuous process for manufacturing a polyolefin resin of improved homogeneity. The invention also relates to a device for carrying out the process.
The manufacture of polyolefin resins by continuous polymerization in a diluent has been known for a long time. Generally, continuous processes comprise the continuous introduction of an olefin, a catalyst and a diluent into a polymerization reactor and the continuous removal from this reactor of a suspension comprising polyolefin particles and the diluent. These continuous manufacturing processes generally lead to resins whose polymer particles have a certain size distribution as a function of the residence time in the polymerization reactor. The particles of different sizes often also have different properties, such as, for example, the melt flow index and the content of catalytic residues. These properties consequently differ from the average properties of the polyolefin resin obtained, which may pose problems during segregation of resins during transportation or storage. Furthermore, the known manufacturing processes generally give an appreciable fraction of fine particles, which may be detrimental to the storage and to the subsequent use of the resins.
The present invention is directed towards providing a process which does not have the abovementioned drawbacks.
The invention consequently relates to a continuous process for manufacturing a polyolefin resin of improved homogeneity, according to which:
(a) in a polymerization reactor (R) comprising a diluent (D), an olefin is polymerized continuously in the presence of a catalyst to produce a suspension (S) comprising the said diluent (D) and polyolefin particles,
(b) a portion of the suspension (S) is taken from the reactor (R),
(c) the suspension taken is transferred into a hydrohydrocyclone separator in which a flow (F) comprising diluent (D) and polyolefin particles, on the one hand, and a concentrated suspension (CS) of polyolefin particles, on the other hand, are formed and separated,
(d) the flow (F) is taken from the hydrohydrocyclone separator and recycled into the polymerization reactor (R), into step (a),
(e) the concentrated suspension (CS) is taken from the hydrohydrocyclone separator and introduced into a subsequent polymerization reactor (Rxe2x80x2), fed with olefin to continue the polymerization and to produce a suspension (Sxe2x80x2) comprising the diluent (D) and polyolefin particles,
(f) a portion of the suspension (Sxe2x80x2) is taken from the subsequent polymerization reactor (Rxe2x80x2),
(g) the suspension taken is transferred to a hydrocyclone separator in which a flow (Fxe2x80x2) comprising diluent (D) and polyolefin particles, on the one hand, and a concentrated suspension (CSxe2x80x2) of polyolefin particles, on the other hand, are formed and separated,
(h) the flow (Fxe2x80x2) is taken from the hydrocyclone separator and recycled into the polymerization reactor (R), into step (a),
(i) the suspension (CSxe2x80x2) is taken from the hydrocyclone separator and the polyolefin particles are separated from the suspension (CSxe2x80x2).
In the present invention, the term xe2x80x9cpolyolefinxe2x80x9d is intended to denote both the homopolymers of an olefin and the copolymers of an olefin with one or more other olefins or other comonomers that are copolymerizable with the olefin.
The olefin used in the polymerization steps (a) and (e) of the process according to the invention is generally chosen from olefins containing from 2 to 12 carbon atoms, and mixtures thereof. The olefin is preferably chosen from 1-olefins containing from 2 to 8 carbon atoms, more particularly from ethylene, propylene, 1-butene, 1-methylpentene, 1-hexene and 1-octene, and mixtures thereof. The olefin used in the subsequently polymerization reactor (Rxe2x80x2), in step (e), is the same as that used in the polymerization reactor (R), in step (a).
It goes without saying that in the polymerizations in steps (a) and (e) of the process according to the invention, besides the olefin, at least one other comonomer that is copolymerizable with the olefin may be used so as to manufacture copolymers. The comonomers are usually chosen from conjugated or unconjugated olefins and diolefins, containing from 2 to 12 atoms. The 1-olefins containing from 2 to 8 carbon atoms as described above give good results. When one or more comonomers are used, it is preferred to use the same comonomer(s) in the polymerization reactors in steps (a) and (e). The amounts of comonomer used in steps (a) and (e) are preferably controlled such that the comonomer/olefin molar ratio in the subsequent polymerization reactor (Rxe2x80x2), in step (e), is between 80% and 120% by weight of the comonomer/olefin molar ratio in the polymerization reactor (R), in step (a).
The diluent (D) used in the process according to the invention may be any diluent which is liquid under the polymerization conditions and in which most of the polymer formed is insoluble under the polymerization conditions. Hydrocarbons are suitable diluents. Aromatic and aliphatic cyclic hydrocarbons containing from 5 to 12 carbon atoms, such as toluene and cyclohexane, are suitable. Preferred diluents are acyclic aliphatic hydrocarbons containing from 3 to 8 carbon atoms, such as pentane and hexane. Propane and isobutane are particularly preferred.
According to one particular case, the diluent may be the olefin itself maintained in liquid form under its saturation pressure.
In another particular case, the diluent may be maintained in its supercritical state.
The polymerization carried out in step (a) of the process according to the invention is carried out in the presence of a catalyst. Any catalyst allowing the polymerization of olefins may be used. Examples of such catalysts which may be mentioned are catalysts of the Ziegler type, vanadium-based or chromium-based catalysts, metallocene catalysts and catalysts based on transition metals from groups 8 to 12 of the Periodic Table of the Elements. These catalysts may be supported on an inorganic or polymeric support. Good results have been obtained with a chromium catalyst supported on a support comprising silica.
The polymerization carried out in step (e) of the process according to the invention is preferably carried out without any fresh catalyst being added to the reactor. Specifically, the concentrated suspension (CS) of polyolefin particles introduced into the subsequent polymerization reactor (Rxe2x80x2) generally still contains enough active catalyst from the reactor (R) to continue the polymerization.
It goes without saying that, in the polymerizations in steps (a) and (e) of the process, besides the olefin(s) and the diluent, other compounds may be present, in particular cocatalysts and agents for regulating the molecular mass, such as hydrogen.
When a cocatalyst is added, it is preferably added only into the polymerization reactor (R), in step (a).
When a regulating agent is added, it is preferable to add the same regulating agent into the polymerization reactors in steps (a) and (e) of the process. The amounts of molecular mass regulating agent are advantageously adjusted such that the regulating agent/olefin molar ratio in the subsequent polymerization reactor (Rxe2x80x2), in step (e), is between 80% and 120% of the regulating agent/olefin molar ratio in the polymerization reactor (R), in step (a). Preferably, the regulating agent/olefin molar ratio is substantially the same in the polymerization reactors in steps (a) and (e).
The polymerization carried out in steps (a) and (e) of the process may take place under very variable temperature and pressure conditions. The polymerization is generally carried out at a temperature of from 20xc2x0 C. to 150xc2x0 C., preferably from 25xc2x0 C. to 130xc2x0 C. Usually, the polymerization is carried out at a pressure of from 105 Pa to 100xc3x97105 Pa, preferably from 10xc3x97105 Pa to 55xc3x97105 Pa.
Usually, the polymerization temperature in step (e) of the process is between 95% and 105% of the polymerization temperature in step (a) of the process according to the invention. Preferably, the difference between the polymerization temperatures in steps (a) and (e) does not exceed 3xc2x0 C. More particularly, the difference does not exceed 1xc2x0 C.
The polymerization carried out in step (a) is carried out in the presence of polyolefin particles, recycled into the reactor (R) via the flows (F) and (Fxe2x80x2). The amount of polyolefin particles recycled into the reactor (R) is generally at least 1% by weight relative to the total weight of polyolefin particles taken from the reactor (R). The amount of particles recycled is usually at least 10%, preferably at least 20%, by weight, relative to the total weight of particles taken from the reactor (R). The amount of particles recycled into the reactor (R) generally does not exceed 95% and preferably does not exceed 60% by weight relative to the total weight of particles taken from the reactor (R).
According to one variant of the process according to the invention, the polymerization carried out in step (a) is carried out in several polymerization reactors connected in series. In this case, the suspension (S) taken from the final reactor of this series of polymerization reactors is transferred into step (b). The suspensions obtained from each reactor preceding the final reactor of the series may be taken and transferred into the next reactor in any known manner. To this end, it may be advantageous also to use hydrocyclone separators. When step (a) is carried out in several reactors in series, the flow (F) may be recycled into the final reactor of this series of polymerization reactors. According to one advantageous embodiment, the flow (F) is recycled into a polymerization reactor preceding this final reactor.
In step (b) of the process according to the invention, a portion of the suspension (S) formed in the reactor (R) in step (a) is taken from this reactor. The amount of suspension taken from the reactor (R) can vary within a wide range. Generally, the amount of suspension taken from the reactor (R) is adjusted so as to correspond to the production of polymer.
In step (b), the suspension is preferably taken continuously from the polymerization reactor (R).
In step (c) of the process according to the invention, the suspension taken from the reactor (R) in step (b) is transferred into a hydrocyclone separator in which a concentrated suspension (CS) of polyolefin particles, on the one hand, and a flow (F) comprising polyolefin particles and diluent (D), on the other hand, are formed and separated.
For the purposes of the present invention, the term xe2x80x9chydrocyclone separatorxe2x80x9d is intended to denote any apparatus which, under the action of a centrifugal force, makes it possible to separate from a suspension of solid particles, on the one hand a liquid flow depleted in solid particles, and on the other hand a flow concentrated in solid particles. Such items of apparatus are well known and are described in particular in Perry""s Chemical Engineers"" Handbook, McGraw-Hill 7th Edition, 1997, pages 19-24 to 19-28. It goes without saying that in the process according to the invention, several hydrocyclone separators may be mounted in series.
The pressure and temperature values in the hydrocyclone separator are generally adjusted such that most of the diluent present remains in liquid form. Preferably, the pressure and temperature are of the order of magnitude of those prevailing in the polymerization reactor preceding the hydrocyclone separator.
The functioning of the hydrocyclone separator is generally adjusted such that the flow (F) recycled into the reactor (R), in step (a), comprises from 0.5% to 90% by weight of polyolefin particles relative to the total weight of polyolefin particles present in the suspension taken from the reactor (R) in step (b). The functioning of the hydrocyclone separator may be adjusted by means of control valves mounted on the pipes for taking the flow (F) and the concentrated suspension (CS) from the hydrocyclone separator. Good results have been obtained by adjusting the functioning of the hydrocyclone separator such that the flow (F) recycled into the reactor (R) comprises at least 5% by weight, preferably at least 10% by weight, of polyolefin particles relative to the total weight of polyolefin particles present in the suspension taken from the reactor (R). The amount of polyolefin particles recycled into the reactor (R) in step (a) preferably does not exceed 50% by weight, more particularly 30% by weight, of the total weight of the polyolefin particles present in the suspension taken from the reactor (R).
In step (d) of the process according to the invention, the flow (F) is taken from the hydrocyclone separator and recycled into the polymerization reactor (R). The flow (F) generally contains the finest particles, i.e. those which contain the least amount of polymer. Recycling them into the polymerization reactor (R) makes it possible to increase their residence time in the polymerization reactor so as to monitor the polymerization and to increase their size. The flow (F) may comprise, in addition to the diluent and the polyolefin particles, other compounds present or formed in the polymerization reactor. Generally, the flow (F) comprises compounds present or formed in the reactor which are soluble in the diluent. The flow (F) usually comprises olefin.
In step (e) of the process according to the invention, the concentrated suspension (CS) is taken from the hydrocyclone separator and transferred into a subsequent polymerization reactor (Rxe2x80x2) into which at least one olefin is added to continue the polymerization.
It may be advantageous to add to the subsequent polymerization reactor (Rxe2x80x2) an additional amount of diluent (D) as defined above. According to one variant of the process according to the invention, this amount of diluent is added to the concentrated suspension before it enters the subsequent polymerization reactor (Rxe2x80x2).
According to one variant of the process according to the invention, the polymerization carried out in step (e) is carried out in several polymerization reactors connected in series. In this case, the suspension (Sxe2x80x2) taken from the final reactor of this series of polymerization reactors is transferred into step (f). The suspensions obtained from each reactor preceding this final polymerization reactor may be taken and transferred into the next reactor in any known manner. To this end, it may be advantageous also to use hydrocyclone separators.
After step (e) of the process according to the invention, a suspension (Sxe2x80x2) comprising diluent (D) and polyolefin particles is obtained.
The respective amounts of polyolefin manufactured in steps (a) and (e) of the process according to the invention may vary within a wide range. Generally, the amount of polyolefin manufactured in step (a) of the process is between 20% and 80% by weight, preferably between 30% and 70% by weight, of the total amount of polyolefin produced in the process according to the invention. Generally, the amount of polyolefin manufactured in step (e) of the process is between 20% and 80% by weight, preferably between 30% and 70% by weight, of the total amount of polyolefin produced in the process according to the invention.
In step (i) of the process according to the invention, a portion of the suspension (Sxe2x80x2) present in the reactor (Rxe2x80x2) is taken from the reactor. The amount of suspension taken from the reactor (Rxe2x80x2) may vary within a wide range. Generally, the amount of suspension taken from the reactor (Rxe2x80x2) is adjusted so as to obtain in the concentrated suspension (CSxe2x80x2) an amount of polyolefin particles which corresponds to the total production of polymer.
In step (f), the suspension is preferably taken continuously from the polymerization reactor (Rxe2x80x2).
In step (g) of the process according to the invention, the suspension taken from the reactor (Rxe2x80x2) in step (f) is transferred into a hydrocyclone separator in which a concentrated suspension (CSxe2x80x2) of polyolefin particles, on the one hand, and a flow (Fxe2x80x2) comprising polyolefin particles and diluent (D), on the other hand, are formed and separated.
The functioning of the hydrocyclone separator is generally adjusted such that the flow (Fxe2x80x2) recycled into the reactor (R), in step (a), comprises from 0.5% to 90% by weight of polyolefin particles relative to the total weight of polyolefin particles present in the suspension taken from the reactor (Rxe2x80x2) in step (f). Good results were obtained by adjusting the functioning of the hydrocyclone separator such that the flow (Fxe2x80x2) recycled into the reactor (R) comprises at least 5% by weight, preferably at least 10% by weight, of polyolefin particles relative to the total weight of polyolefin particles present in the suspension taken from the reactor (Rxe2x80x2). The amount of polyolefin particles recycled into the reactor (R) in step (a) preferably does not exceed 50% by weight, more particularly 30% by weight, of the total weight of polyolefin particles present in the suspension taken from the reactor (Rxe2x80x2).
The pressure and temperature values in the hydrocyclone separator are generally adjusted such that most of the diluent present remains in liquid form. The pressure and temperature are preferably of the order of magnitude of those prevailing in the polymerization reactor preceding the hydrocyclone separator.
In step (h) of the process according to the invention, the flow (Fxe2x80x2) is taken from the hydrocyclone separator and recycled into the polymerization reactor (R), i.e. into step (a) of the process. The flow (Fxe2x80x2) generally contains the finest particles, i.e. those which contain the smallest amount of polymer. Recycling them into the polymerization reactor (R) makes it possible to increase their residence time in the polymerization reactors so as to continue the polymerization and to increase their size. The flow (Fxe2x80x2) can comprise, besides the diluent and polyolefin particles, other compounds present or formed in the process. The flow (Fxe2x80x2) generally comprises compounds that are soluble in the diluent. The flow (Fxe2x80x2) usually comprises olefin. In particular, when step (a) is carried out in several polymerization reactors connected in series, the flow (Fxe2x80x2) may be recycled into the final polymerization reactor of this series. According to one advantageous embodiment, the flow (Fxe2x80x2) is recycled into a polymerization reactor preceding the final reactor of this series.
In step (i) of the process according to the invention, the concentrated suspension (CSxe2x80x2) is taken from the hydrocyclone separator and the polyolefin particles present therein are separated from the suspension (CSxe2x80x2). The polyolefin particles may be separated out by any known method. The polymer particles are generally separated from the majority of the diluent by subjecting the concentrated suspension (CSxe2x80x2) obtained from step (g) of the process according to the invention to a treatment under pressure and temperature conditions that are capable of evaporating at least some of the diluent. The polymer particles now containing only a small amount of residual diluent may then be dried by any known means, for example by heating in a drier.
According to a first variant of step (i) of the process according to the invention, the concentrated suspension (CSxe2x80x2) is subjected to a pressure reduction to a pressure below 5xc3x97105 Pa. The diluent evaporated off may then be recondensed by compression in order to be reused in the process according to the invention. Before reusing it, the diluent is usually subjected to a purification so as to remove the majority of the olefin and any other compounds present. After purification, the diluent may be reused in steps (a) and/or (e) of the process according to the invention.
According to a second variant of step (i) of the process according to the invention, the concentrated suspension (CSxe2x80x2) is subjected to a pressure reduction under temperature and pressure conditions which ensure the evaporation of most of the diluent, but which are such that the subsequent cooling of the diluent evaporated at a temperature of less than or equal to 60xc2x0 C. allows it to be recondensed without needing to compress it. The temperature at which the pressure reduction is carried out is generally between 50xc2x0 C. and 90xc2x0 C. In order to adjust the temperature at which the pressure reduction is carried out, it may be advantageous to heat the concentrated suspension (CSxe2x80x2) taken from the hydrocyclone separator by means of a line heater. The pressure at which the pressure reduction is carried out is generally between 5xc3x97105 Pa and 20xc3x97105 Pa. This variant of the process has the advantage that the diluent thus separated from the polymer particles may be recondensed by simple cooling without a compression step and may be reused in step (a) and/or (e) of the process according to the invention. This second variant of step (i) of the process is very advantageous when a diluent which has a boiling point at atmospheric pressure of less than about 25xc2x0 C. is used.
The process according to the invention can be applied to the production of a polyolefin resin. The process according to the invention can advantageously be applied to the production of polyethylene resins. In the present invention, the term xe2x80x9cpolyethylenexe2x80x9d is intended to denote both homopolymers of ethylene and copolymers of ethylene with one or more other comonomers that are copolymerizable with ethylene, as defined above. The process is suitable for obtaining a polyethylene comprising less than 10% by weight, preferably less than 5% by weight, of units derived from another comonomer. Good results have been obtained for the production of a copolymer of ethylene and of units derived from 1-butene and/or 1-hexene.
The process according to the invention has the advantage that it narrows the distribution of the residence times of the various polyolefin particles. The process according to the invention consequently makes it possible to obtain a resin which has good homogeneity. The process especially makes it possible to obtain resins whose polyolefin particle size distribution is narrow. The process according to the invention also makes it possible to obtain resins in which most of the particles have properties very close to the average properties of the resin. The resins obtained in the process according to the invention also have the advantage of containing only a small amount of fine particles, more particularly of particles with a diameter of less 200 xcexcm. In addition, and more especially when a supported chromium-based catalyst is used, the process makes it possible to obtain a very good catalytic yield. The resins thus obtained contain only small amounts of catalytic residues.
The invention also relates to a device for carrying out the process described above, comprising, connected in series, a polymerization reactor (R), a hydrocyclone separator, a circuit for recycling the flow (F) into the reactor (R), a device for removing concentrated suspension (CS), a polymerization reactor (Rxe2x80x2), a hydrocyclone separator, a circuit for recycling the flow (Fxe2x80x2) into the reactor (R) and a device for separating the polyolefin particles from the concentrated suspension (CSxe2x80x2).
Any reactor functioning continuously may be used as polymerization reactor, such as reactors of stirred-tank type or reactors of loop type. Good results have been obtained with loop reactors.
In the process according to the invention, the flow (F) may be taken from the hydrocyclone separator and recycled into the reactor (R) by exploiting a pressure difference prevailing in the polymerization reactor (R). More particularly, when the polymerization reactor is a reactor of the loop type, the suspension (S) may be taken from the reactor and the flow (F) may be recycled into the reactor (R) by exploiting the pressure difference prevailing upstream and downstream of the system for stirring the loop reactor. It is preferred, however, to take the flow (F) from the hydrocyclone separator by creating a pressure difference upstream and downstream of the hydrocyclone separator by means of a circulation pump. The pump is preferably mounted on the circuit for recycling the flow (F) into the reactor (R).
In the process according to the invention, the flow (Fxe2x80x2) may be taken from the hydrocyclone separator and recycled into the reactor (R) by exploiting a pressure difference prevailing between the polymerization reactor (Rxe2x80x2) and the polymerization reactor (R). It is preferred, however, to take the flow (Fxe2x80x2) from the hydrocyclone separator by creating a pressure difference upstream and downstream of the hydrocyclone separator by means of a circulation pump. The pump is preferably mounted on the circuit for recycling the flow (Fxe2x80x2) into the reactor (R).